Methyltrioxorhenium (MTO)

Introduction

Methyltrioxorhenium (1) is an important and versatile catalyst widely studied as an oxygen transfer reagent in oxidation reactions of a variety of substrates. [1] The important features of MTO as a catalyst are its ease of synthesis, commercial availability and stability to air. MTO was firstly synthesized by Beattie and Jones in 1979. [2] Sub­sequently, Herrmann et al. developed a more simple and ­efficient synthesis based on the reaction of dirhenium ­heptoxide with methyltributyltin. [3]

MTO (1) reacts with H₂O₂, the usual stoichiometric ­oxidant, to give equilibria with formation of monoperoxo- and diperoxo-rhenium(VII) species (2 and 3, respectively). [4] The latter confers a characteristic yellow color to the solution and it is the most reactive towards oxygen-accepting substrates.

The MTO/H₂O₂ system makes use of nontoxic reagents, the oxidation and work-up procedures are very simple, water is the only byproduct, and non-aqueous solvent can be used if UHP (urea-hydrogenperoxide adduct) is used instead of H₂O₂ as the stoichiometric oxidant.

References

• For reviews, see:
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• 1b Owens S. Arias J. Abu-Omar MM. Catal. Today  2000,  55:  317 
• 1c Kuhn FE. Herrmann WA. Chemtracts  2001,  14:  59 
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